Aromatic polyepoxide-modified oxyalkylated phenol-aldehyde resins



2 (llaims. ((31. 260-43) The present application is a continuation-in-part of our co-pending application, Serial No. 343,804, filed March 20, 1953, now abandoned, and a division of our copending application Serial No. 393,221, filed November 19, 1953, now US. Patent No. 2,819,212, dated January 7, 1958. Said first mentioned aforementioned co-pending application is concerned with processes for breaking petroleum emulsions of the water-in-oil type employing a demulsifier including the reaction products of (A) certain oxyalkylated phenol-aldehyde resins, therein described in detail, and (B) certain phenolic polyepoxides and cogenerically associated compounds formed in their preparation, also therein described in detail, the ratio of reactant (A) to reactant (B) being in the proportion of two moles of (A) to one mole of (B).

The present invention relates to new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. The new products are the reaction products of the above described reactants (A) and (B), which are hereinafter described in detail, the ratio of reactant (A) to reactant (B), however, being in the proportion of four moles of (A) to three moles of (B).

The present application thus differs from the aforemen tioned application in that one obtains products having at east twice the molecular weight by the use of a molal ratio of 4 moles of (A) to 3 moles of (B). Specifically, the product described in aforementioned co-pending application may be indicated thus:

In contradistinction the products herein described and useful for the resolution of petroleum emulsions may be indicated thus:

Products may be obtained by either a continuous process involving the two reactants or, if desired, by a two step method in which the final product described in aforementioned co-pending application becomes an intermediate and is in ratio of two moles of intermediate to one mole of (B), thus:

In our co-pending application, Serial No. 393,222, filed November 19, 1953, now US. Patent No. 2,792,355, reference is made to another product in which two different polyepoxides are employed; in other words, if the one described above is referred to as (B) and is essentially hydrophobe in character, then in comparision our aforementioned copending application, Serial No. 393,222, is concerned with a combination obtained by a stepwise process comparable to the one last mentioned above in which final addition of (B) is replaced by the addition of a hydrophile polyepoxide and thus is illustrated in the following manner;

ice

For an obvious reason, to wit, ease of comparison with both of the aforementioned applications, Serial No. 343,804 and Serial No. 393,222, we are describing the 2- step process of manufacture although obviously the two steps could be fused or combined to be a single step, provided the same polyepoxide or the same type of polyepoxide, for instance, an essentially hydrophobe polyepoxide, is used. The single step procedure is illustrated subsequently.

Notwithstanding the fact that subsequent data will be presented in considerable detail, yet the description becomes somewhat involved and certain facts should be kept in mind. The polyepoxides, and particularly the diepoxides may have no connecting bridge between the phenolic nuclei as in the case of a diphenyl derivative, or may have a variety of connecting bridges, i.e., divalent linking radicals. Our preference is that either diphenyl compounds be employed or else compounds where the divalent link is obtained by the removal of a carbonyl oxygen atom as derived from a ketone or aldehyde.

If it were not for the expense involved in preparing and purifying the monomer we would prefer it to any other form, i.e., in preference to the polymer or mixture of polymer and monomer.

Stated another way we would prefer to use materials of the kind described, for example, in US. Patent 2,530,353, dated November 14, 1950. Said patent describes compounds having the general formula wherein R is an aliphatic hydrocarbon bridge, each n independently has one of the values 0 and 1, and X is an alkyl radical containing from 1 to 4 carbon atoms.

The compounds having two oxirane rings and employed for combination with the oxyalkylated phenol-aldehyde resin are characterized by the following formula and cogenerically associated compounds formed in their preparation:

in which R represents a divalent radical selected from the class of ketone residues formed by the elimination of the ketonic oxygen atom and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical the divalent radical, the divalent sulfone radical, and the divalent monosulfide radical S, the divalent radical and the divalent disulfide radical S-S-; and R 0 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol III .3 in which R, R", and R' represent hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; n represents an integer including zero and 1, and n represents a whole number not greater than 3. The above mentioned componnds and those cogenerically associated compounds formed in their preparation are thermoplastic and organic solvent-soluble. Reference to being thermoplastic characterizes products as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus difierentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents, such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with the resin. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as, for example, kerosene, benzene, toluene, dioxane, various ketones, chlorinated solvents,

4 a thermoplastic solid, and additionally even may be watersoluble.

Having obtained a reactant having generally 2 epoxy rings as depicted in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any one of a number of oxyalkylated resins which are still oxyalkylation-susceptible. There is available considerable literature, particularly patent literature dealing with oxyalkylated resins of the kind herein employed for reaction with the selected polyepoxides. These will be referred to in greater detail subsequently. For purpose of convenience, reference is simply made at the moment to the following patents: U.S. Patent Nos. 2,499,365; 2,499,366; 2,499,367; 2,499,368; and 2,499,370, all dated March 7, 1950, to De Groote and Keiser.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i.e., the compound having two oxirane rings and oxyalkylated resins as described. Proceeding with the example previously described it is obvious the reaction ratio of two moles of the oxyalkylated resin to one mole of the diepoxide gives a product which may be indicated as follows:

(oxyalkylated resin) dibutyl ether, dihexyl ether, ethyleneglycol diethylether, in which the various characters have their prior signifidiethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter, the word epoxy, unless indicated otherwise, will be used to mean the oxirane ring, i.e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2- epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of a strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane (1,2-3 ,4-diepoxybutane) It well may be that even though the previously suggested formula represents the principal component, or components, of the result or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides whichare polyether derivatives of polyhydric phenols containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. See U.S. Patent No. 2,494,- 295, dated January 10, 1950, to Greenlee. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instantinvention is directed towards products which are not resins and have certain solubility characteristics not inherent in resins. Note, for example, that said U.S. Patent No. 2,494,295 describes products wherein the epoxide derivative can combine with a sulfonamide resin. The intention in said U.S. Patent 2,494,295, of course, is to obtain ultimately a suitable resinous product having the characteristics of a comparatively insoluble resin. The intent in the present instance in a comparable example would be to use a sulfonamide (not a sulfonamide resin) and obtain a material which does not have the characteristics of an ordinary varnish resin or the like, i.e., is permanently soluble, and stays soluble generally as a liquid of ordinary viscosity, or as a thick viscous liquid and may be cance. However, molal ratios may be varied as noted subsequently.

Such products must be soluble in suitable solvents such as a non-oxygenated hydrocarbon solvent or an oxygenated hydrocarbon solvent or, for that mater, a mixture of the same with water. Needless to say, after the resin has been treated with a large amount of ethylene oxide the products are water soluble and may be soluble in an acid solution.

The purpose in this instance is to differentiate from insoluble resinous matrials, particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or at least distinct dispersibility in water. For instance, the products freed from any solvent can be shaken with five to twenty times their weight of distilled water at ordinary temperature and are at least self-dispersing, and in many instances water-soluble, in fact colloidally soluble.

Basic nitrogen atoms can be introduced into such derivatives by use of a reactant having both a nitrogen group and a 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U.S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

As far as the use of the herein described products goes for the purpose of resolving petroleum emulsions of the water-in-oil type, and also for that matter for numerous other purposes where surface active materials are effective, and particularly for those uses specified elsewhere herein, we prefer to employ oxyalkylated derivatives, which are obtained by the use of monoepoxides, in such manner that the derivatives so obtained have sufiicient hydrophile character to meet at least the test set forth in U.S. Patent No. 2,499,368 dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a waterinsoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various oxyalkylated derivatives obtained particularly by use of ethylene oxide, propylene oxide, etc. may not necessarily be xylene-soluble although they are xylene-soluble in a large number of instances. If such compounds are not xylene-soluble the obvious chemical equivalent, or equivalent chemical test,

can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test obviously is the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

Reference is made again to US. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. Attention is directed to that part of the text which appears in columns 28 and 29, lines 12 through 75, and lines 1 through 21, respectively. Reference is made to this text with the same force and effect as if it were herein included. This, in essence, means that the preferred product for resolution of petroleum emulsions of the water-in-oil type is characterized by the fact that a 50-50 solution in xylene or its equivalent, when mixed with one to three volumes of water and shaken, will produce an emulsion.

For purpose of convenience what is said hereinafter will be divided into eight parts with Part 3, in turn, being divided into three subdivisions, and Part 6, in turn, being divided into two subdivisions.

Part 1 is concerned with our preference in regard to the polyepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

Part 3, Subdivision A, is concerned with the preparation of monomeric diepoxides, including Table I;

Part 3, Subdivision B, is concerned with the preparation of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with suitable phenol-aldehyde resins to be employed for reaction with the epoxides;

Part 5 is concerned with the oxyalkylation of the previously described phenol-aldehyde resins;

Part 6, Subdivision A, is concerned with the Z-step procedure involving reaction between the two preceding I types of materials and examples obtained by such reactions. It involves in essence, preparation of an intermediate by reaction between 2 moles of the oxyalkylated phenol-aldehyde resin and one mole of the diglycidyl ether, for example (identical with the products described in aforementioned co-pending application, Serial No. 343,804), followed by a second step in which 2 moles of these larger molecules are combined with use of a single mole of a diglycidyl ether or the like;

Part 6, Subdivision B, is a single step procedure resulting in substantially the same compounds by the use of 4 moles of the oxyalkylated phenol-aldehyde resin and 3 moles of the diglycidyl ether, or the equivalent;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

Part 8 is concerned with uses for the products herein described, either as such or after modification, including uses in applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solventsoluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus,

the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the epoxides usually results in the formation of a cogeneric mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at a low cost, or if they could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances Where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, and the materials obtained by reacting subst-ituted monofunctional phenols with an aldehyde illustrate the third class. All the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our preference is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for this compound is H H H H H H O JJH 0 Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the 4,4-isomers predominating and with lesser quantities of the 2,2 and 4,2'-isorners being present. It is immaterial which one 7 of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, to wit, Part 1, and in succeeding parts, the

text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of one compound for the other would be required. Thus, What is said hereinafter, although directed to one class or a few classes, applies with equal force and effect to the other classes of epoxide reactants.

If sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a low-molal sulfur-containing compound can react with epichlorohydrin there produce these materials free from coge'neric materials of related composition. For a discusstion of these difiicul ties, reference is made to U.S. Patent No. 2,819,212, beginning at column 7, line 21.

PART 3 Subdivision A TABLEI Patent Diphenol Diglycidylether reference 0112(06114011): Di(epoxypropoxyphe yllmethane 2,506,486 OH3CH(GQHQOH)Z Di(epoxypropoxypheuyl)methylmethane 2, 506, 480 gCHmG (C0H4OH D1(epoxyoropoxyphenyl)dimethylmethaue. 2, 500. 486 11150 (CH3) (U6114011) D1(epoxypropoxyphenyl)ethylmethylmethane. 2, 506, 480 (C2H5)2C (CuH;OH) Di (epoXypropoxy-phenyl)dietnylmethane 2, 500, 486 01130 (03H?) (OsHiOH) Di(epoxypropoxyphenyDmethylpropylmethane. 2, 506, 486 (EH (O H (CgH4OH) Di (epoxypropoxyphenyl)methylphenylmethnne 2, 506. 480 Gil-I50 (OsH5) (CdHiOH) D1(epoxypropoxypheuyDethylphenylmethane. 2, 506, 486 031110 (CtlHs) (CoHiOH) Di(epotypropoxyphenyl)propylphenylmethau 2, 500, 486 C4HQC(CBH5)(CGH;OH)Q D (epoxypropoxyphenyl)butyiphenylmethane 2,500,480 (CH3C H4)CH(C H4OH) D (epoxypropoxyphenyDtolylrue ane 2,500,486 (GH3GGH4)C(CHs) (CaHH)2 D1(cpoxypropoxyphenyl)tolylmethylrnethanc 2, 500, 486 Dihydroxy dipheuyl 4,4-lus(2,3-ep0xypr0poxy)diphen 2,530,353 (CH;)G(C;H .O H OH)1 2,2-bis(4-(2,3-epoxypropoxy)2-tertiarybutylphenyDpropane..- 2,530,353

may be formed a by-product in which the chlorine happened to be particularly reactive and may represent a product, or a mixture of products, which would be unusually toxic, even though incomparatively small concentrati0n. 7

PART 2 The polyepoirides and particularly the diepoxides can be derived by more than one method as, for example, the use of epichlorohydrin or glycerol dichlorohydrin.

A number of problems are involved in attempting to PART 3 Subdivision B As to the preparation of low-molal polymeric epoxides or mixtures reference is made to numerous patents and particularly the aforementioned U.S. Patents Nos. 2,575,558 and 2,582,985.

In light of the aforementioned U.S. Patent No. 2,575,558, the following examples can be specified by reference to the formula therein provided one still bears in mind it is in essence an over-simplification.

TABLE II 0 H v 0 C C C OR [R] R0 C C OR [R] R0 0 C C w 1' D l H: r-rm Hil Hi 1 11111 H.

OH n (in which the characters have their previous significance) Example R10" iromHRi OH -R- n n Remarks number B1 Hydroxy benzene CH; 1 0,1,2 Phenol known as bis-phenol A. Low polymeric mixture about 36 or more where n=0, remainder largely where (E 11.:1, some where 'n'=2.

B2 .-.do CH; 1 0,1,2 Phenol knownas bis-phenolB. Seenote Cl} regarding B1 above.

I 5 CH:

B3 Orthobutylphenol on, 1 0,1,2 Even though at is preferably 0, yet the I usual reaction product might well con- -C- tam materials where n is 1, or to a ll lesser degree 2.

B4 Orthbamylphenol CH3 1 0,1,2 Do.

TABLE II-Contlnued Example R1O- from HRrOH -R n n Remarks number B5 Orthooetylphenol CH5 1 0,1,2 Even though 12 is preferably 0, yet the I usual reaction product might well con- -C-- tein materials where n is 1, or to a l: tesser degree 2.

B6 Orthononylphenol CH: 1 0,1,2 Do.

B7 Orthododecylphenol CH; 1 0,1,2 Do.

B8 Metaeresol CH: 1 0,1,2 See prior note. This phenol used as l initial material is known as bis-phenol -C O, For other suitable bis-phenols see i U. S. Patent 2,564,191. CH3

B9 do.- (3H3 1 0, 1, 2 See prior note.

C (:JH: CH2

B10 Dibutyl (ortho-pare) phenol. I01 1 0,1,2 Do.

B11 Diamyl (ortho-para) phenol. 1(1; 1 0,1,2 Do.

: H B12 Dioetyl (ortho-para) phenol- 1% 1 0,1,2 Do.

1313 Dinonyl (ortho-para) phenol. 1(13 1 0,1,2 Do.

1314 Diemyl (ortho-pore) phenol. 1g 1 0,1,2 Do.

B15 d0 g 1 0,1,2 DO- B16 Hydroxy benzene (I) 1 0,1,2 Do.

B17 Dlamyl phenol (ortho-para). -S--S- 1 0,1,2 Do.

1318 -do S 1 0,1, 2 Do.

B19 Dibutyl phenol (ortho-para). 1 1 0,1,2 Do.

B20 do H H 1 0,1,2 I DO.

B21 Dinonylphenol(ortho-pera)- 1 01 13 1 0,1,2 Do.

B22 Hydroxy benzene (3l 1 0,1,2 D0.

B23 "do None 0 0,1,2 Do. B24 Ortho-isopropyl phenol CH5 1 0,1,2 See prior note. (As to preparation of 4,4- isopropylidene bis-(z'isopropylphenol) C see U. S. Patent No. 2,482,748, dated l Sept. 27, 1949, to Dietzler.) CH3 B25 Pera-octyl phenol CH2SCH2 1 0,1,2 See prior note. (As to preparation of the phenol sulfide see U. S. Patent No. 2,488,134, dated NOV. 15, 1949, Mikeska et a1.)

B26 Hydroxybenzene CH3 1 0,1,2 See prior note. (As to preparation of the phenol sulfide see U. S. Patent No. --C 2,526,545.)

e (I) CzHE 1 1 Subdivision C The prior examples have been limited largely to those in which there is no divalent linking radical, as in the case of diphenyl compounds, or where the linking radical is derived from a ketone or aldehyde, particularly a ketone. Needless to say, the same procedure is employed in converting diphenyl into a diglycidyl ether regardless of the nature of the bond between the two phenolic nucl i. For purpose of illustration attention is directed to-numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant.

As previously pointed out the initial phenol may be substituted, and the substituent group in turn may be a cyclic group such as the phenyl group or cyclohexyl group as in the instance of cyclohexylphenol or phenylphenol. Such substituents are usually in the ortho position and may be illustrated bya phenol of the following composition:

ism

HO --OH Similar phenols which are monofunctional, for instance, paraphenyl phenol or paracyclohexyl phenol with an additional substituent in the ortho position, may be employed in reactions previously referred to, for instance, with formaldehyde or sulfur chlorides to give comparable phenolic compounds having 2 hydroxyls and suitable for subsequent reaction with epichlorohydrin, etc.

Other samples include:

CsHn s u in which the -C H groups are secondary amyl groups. See US. Patent No. 2,504,064.

12 See U.S. Patent No. 2,285,563.

H OH\;H/CH; CHr-CH CH3 Q -O- a CH:

CH: OBI-Cg: om CH:

GHQ-UH: See US. Patent No. 2,503,196.

r HO-O-C 013'.

(:JH: I R

wherein R is a member or the group consisting of alkyl,

and alkoxyalkyl radicals containing from 1 to 5 carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U.S. Patent No. 2,526,545.

wherein R is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R is a s'ubstituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See US. Patent No. 2,515,906.

See Us. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

Alkyl Alkyl in which R is a methylene radical, or a substituted methylene radical which represents the residue of an aldehyde and is preferably the unsubstituted methylene radical derived from formaldehyde. See US. Patent No. 2,430,002.

See also US. Patent No. 2,581,919 which describes di(dialkyl cresol) sulfides which include the monosulfides,

T3 the disulfides, and the polysulfides. The following formula represents the various dicresol sulfieds of this invention:

OH /CH3 CH3 OH R2 in which R and R are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R and R each preferably contain 3 to about carbon atoms, and x is l to 4. The term sulfides as used in this text, therefore, includes monosulfide, disulfide, and polysulfides.

.' PART 4 This part is concerned with the preparation of phenolaldehyde resins of the kind described in detail in U.S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualifications; said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. For the present purpose the substituent may have as many as 18 carbon atoms, as in the case of resins prepared from tetradecylphenol, substantially para-tetradecylphenol, commercially available. Similarly, resins can be prepared from hexadecylphenol or octadecylphenol. This feature will be referred to subsequently.

In addition to U.S. Patent No. 2,499,370, reference is made also to the following U.S. patents: Nos. 2,499,365; 2,499,366 and 2,499,367, all dated March 7, 1950, to De Groote and Keiser. These patents, along with the other two previously mentioned patents, described phenolic resins of the kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are most satisfactory, with the additional C carbon atom also being very satisfactory. The increased cost of the C and C carbon atom phenol renders these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methods of preparing resins useful as intermediates for preparing the products of the present application, and reference is made to that patent for such detail description and to Examples 1a through 103a of that patent for examples of suitable resins.

As previously noted, the hydrocarbon substituent in the phenol may have as many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphenol and octadecylphenol, reference in each instance being to d-ifunctioual phenol, such as the orthoor para-substituted phenol or a mixture of the same. Such resins are described also in issued patents, for instance, U.S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser, such as Example 7111.

It is sometimes desirable to present the resins herein employed in an over-simplified form which has appeared from time to time in the literature, and particularly in the patent literature for instance, it has been stated that the composition is approximated in an idealized form by the formula radical having from 4 to 14 carbon atoms, such as butyl,

amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

in the above formula the aldehyde employed in the resin manufacture is formaldehyde. Actually, some other aldehyde such as acetaldehyde, propionaldehyde, or butyraldehyde may be used. The resin unit can be exemplified thus:

R R n R in which R' is the divalent radical obtained from the particular aldehyde employed to form the resin.

As previously stated, the preparation of resins, the kind herein employed as reactants, is Well known. See U.S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. Resins can be made using an acid catalyst or basic catalyst or a catalyst showing neither acid nor basic properties in the ordinary sense or Without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i.e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For purpose of convenience suitable resins are characterized in the following table:

TABLE III E R hlfoi. wt. 1- resin ample R if derived as molecule number from- (based on n+2) Phenyl Para Formal- 3. 5 992. 5

dehyde Tertiary butyl I do ...do 3. 5 882. 5 Secondary butylI Ortho d0 3.5 882.5 O vcloher' l Para. do 3.5 1, 025.5 Tertiary amyl .d0. d0 3. 5 959. 5 Mixed secondary Orth0 do 3.5 805.5

and tertiary amyl. Propyl 3.5 805.5 Tertiary hex 3. 5 1, 36. 5 Octyl 3. 5 1, 190. 5 Nony 3.5 1,267.5 DecvL.-. d 3. 5 1, 344. 5 Dodecyl 0--.- do 3.5 1,498.5 13a Tertiary butyl 0"... Ariptglde 3.5 945.5 3.5 1, 022. 5 Nonyl 3. 5 1. 330. 5 Tertiary butyl 3. 5 1,071. 5

17a Tertiary amyl 3. 5 1,148.5 1811 Nony do. .do 3.5 1,456.5 19a Tertiary butyl o Propional- 3.5 1,008.5

dehyde. 20a Tertiary arnyl .do ..do 3.5 1, 085. 5 21a onyl do do 3.5 1,393.5 22a Tertiary butyl do Formal- 4.2 996.6

dehyde.

We have prepared such a similar TABLE V TABLE IV--Contlnued parison, blanks appear in the above ppear in previously mentioned tables in U. S.

TABLE III Oxypropylated derivatives comparable to 1b through 801) as described above can readily be obtained by substituting a molar equivalent amount of proplyene oxide,

Nora-For ease of com table where blanks a Patent 2, 581, 376.

i.c., 56 lbs. of propylene oxide, for example, for each 44 lbs. of ethylene oxide. series but for sake of brevity only a few will be included for purposes of illustration. oxide, 60

Resin, ylene Solvent, lbs.

TABLE IV Aldehyde g to the tables beginning in column 21 of 50 ,376 and extending through column 36.

Phenol y amyl. Forlgialdehyde- 0 do We have simply numbered these products beginning with 1b, allotting, of course, five numbers to each table beginning with the first table. For convenience these sixteen tables are summarized in the following table:

already described in detail in the patent literature, we

US. Patent 2,581

are referrin TABLE V Continued It will be noted that, the various resins referred to in SI P the aforementioned US. Patent 2,499,370 are substanmnple g Phenol Aldehyde 3 5 Resin; igs, tially the same type of materials as referred to in Table I. No. a te d lbs. lbs. Ogle, For instance, resin 31; of the table is substantially the same a 5 as 2;: of the patent; resin a of the table is substantially 1 the same as 34a of the patent; and resin 38a of the table is 770..... 7%.... Para-tertiary Fnlrg rtiiilde- 9.52 12. 24 16.45 m as 31 of the p V n I I 22-60 In reaction with polyepoxides, and particularly di- 3.43 18.55 egoxides, a large 7 number of the previously described H v I v s I 1 oxyalkylated resins have been ernployed. For conven- As an illustration of oxypropylated resins involving the ience, the following list is selected indicating the previuse of both ethylene and propylene oxide, reference is ously described compounds and their molecular weights. made to the aforementioned U.S. Patent 2,557,081, dated Such resins are generally employed as a solution and June 19, 1-95 1, to De Groote and Keiser. The last table the polyepoxide employed is a 50% solution, usually both in column 28 of said patent describes in detail the prepara- 15 reactants being dissolvedin grylene and sufficient sodium tion of a series of oxyalkylated resins in which both promethylate added to act as a catalyst, for instance, 1 to 2%.

TABLE V:

See U. S. Pat. 2,557,081

Ethylene Propylene Flake Ex. No. Point; Resin used Resin, oxide, oxide, Weight caustic Ex. No. on lbs. lbs. lbs. of Xylene soda,

in graph ounces above on patent above Te'1't(i amylphenol formaldehyde- 0 cauwwv-n cecncncamwwwwwmammwwlwuu'a pylene and ethylene oxide are employed. Simply by way of illustration a series of 27 compounds are included, the descriptions of which appear in detail in said aforementioned US. Patent 2,557,081 to De Groote and Keiser. Note the first series of nine compounds, ld through 9d, were prepared with a propylene oxide first and then ethylene oxide. The second 9, 10d through 18d inclusive, were prepared using ethylene oxide first and then propylene oxide, and the last 9, 19d through 27d, were prepared by random oxyalkylation, i.e., using a mixture of the two oxides.

In the preparation of the resins our preferences to use hydrocarbon substituted phenols, particularly para-substituted, in which the substituted radical R contains 4 to 18 carbon atoms and particularly 4 to 14 carbon atoms. The amount of alkylene oxide introduced may be comparatively large in comparison to the initial resin. For instance, there may be as much as 50 parts by weight of. an oxide or mixed oxides used for each part by weight of resin employed.

TABLE VII Molecular weight Example number 1 9 PART SIX Subdivision A As previously pointed out, having the two types of reactants, i.e., the oxyalkylated phenol-aldehyde resins and the diglycidyl ethers or their equivalent, one can then proceed with either a single step reaction combining 4 moles of the oxyalkylated derivative with 3 moles of the diglycidyl ether or else one can employ a 2-step process in which one first combines 2 moles of the oxyalkylated phenol-aldehyde resin with one mole of the ether and then subsequently combines this product, which may be considered as an intermediate, with another mole of ether in the combination of 2 moles of the intermediate plus one mole of diglycidyl ether. For reasons previously indicated the instant part, i.e., Subdivision A, is concerned with a 2-step process. As noted above in the 2-step process the reactions which result in the formation of an intermediate involve two moles of an oxyalkylated phenolaldehyde resin of the kind previously described and one mole of a diglycidyl ether as specified. The reactionjs essentially an oxyalkylation reaction and thus may be considered as merely a continuance of the previous oxyalkylation reaction. The previous oxyalkylation reaction involved a monoepoxide as difierentiated from a polyepoxide and particularly a diepoxide. place in substantially the same way, i.e., by the opportunity to react at somewhere above the boiling point of water and below the point of decomposition; for example, 130-185 C. in the presence of a small amount of alkaline catalyst. Since the polyepoxide is non-volatile as compared, for example with ethylene oxide, the reaction is comparatively simple. Purely from a mechanical standpoint it is a matter of convenience to conduct both classes of reactions in the same equipment. In other words, after the phenol-aldehyde resin has been reacted with ethylene oxide, propylene oxide or the like, it is subsequently reacted with a polyepoxide. The polyepoxide reaction can be conducted in an ordinary reaction vessel such as the usual glass laboratory equipment. This is particularly true of the kind used for resin manufacture as described in a number of patents as, for example, U.S. Patent No. 2,499,365. One can use a variety of catalyst in connection with the polyepoxide of the same class employed with monoepoxide. In fact, the reaction will go at an extremely slow rate without any catalyst at all. The usual catalyst include alkaline materials such as caustic soda, caustic potash, sodium methylate, etc. Other catalysts may be acidic in nature and are of the kind characterized by iron and tin chlorides. Furthermore, insoluble catalysts such as clays or specially prepared mineral catalysts have been used. For practical purposes, it is best to use the same catalyst as is used in the initial oxyalkylation step and in many cases there is sufficient residual catalyst to serve for the reaction involving the second oxyalkylation step, i.e., the polyepoxide. For this reason, we have preferred to use a small amount of finely divided caustic soda or sodium methylate as the initial catalyst and also the catalyst in the second stage. The amount generally employed is 1, 2, or 3% of these alkaline catalysts.

Actually, the reactions of polyepoxides with various resin materials have been thoroughly described in the literature and the procedure is, for all purposes, the same as with glycide which has been described previously.

It goes without saying that the reaction involving the polyepoxide can be conducted in the same manner as the monoepoxide as far as the presence of an inert solvent is concerned, i.e., one that is not oxyalkylanon-susceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent,

The reactions take or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The solvent so selected should be one which, of course, is suitable in the oxyalkylation step involving the monoepoxides described subsequently. The solvent selected may depend on the ability to remove it by subsequent distillation if required. Here again it has been our preference to have a solvent present in the oxyalkylation involving the initial stage and permitting the solvent to remain. The amount of solvent may be insignificant, depending whether or not exhaustive oxyalkylation is employed. However, since the oxyalkylated phenol aldehyde resins are almost invariably liquids there is no need for the presence of a solvent as when oxyalkylation involves a solid which may be rather high melting. Thus, it is immaterial whether there is solvent present or not and it is immaterial whether solvent was added in the first stage of oxyalkylation or not, and also it is immaterial whether 'there was solvent present in the second stage of oxyalkylation or not. The advantage of the presence of solvent is that sometimes it is a convenient way of controlling the reaction temperature and thus in the subsequent examples we have added sufiicient xylene so as to produce a mixture which boils somewhere in the neighborhood of to C. and removes xylene so as to bring the boiling point of the mixture to about 140 C. during part of the reaction and subsequently removing more xylene so that the mixture refluxed at somewhere between to C. This was purely a convenience and need not be employed unless desired.

Example la The oxyalkylated resin employed was the one previously identified as 2b, having a molecular weight of 2169; the amount employed was 217 grams. The resin was dissolved in approximately an equal weight of xylene. The mixture was heated to just short of the boiling point of water, Le, a little below 100 C. Approximately onehalf percent of sodium methylate was added, or, more exactly, 1.1 grams. The stirring was continued until there was a solution or distribution of the catalyst. The mixture was heated to a little past 100 C. and left at this temperature while 17 grams of the diepoxide (previously identified as 3a), dissolved in an equal weight of xylene, were added. After the diepoxide was added the temperature was permitted to rise to approximately 107 C. The time required to add the diepoxide was approximately onehalf hour. The temperature rose in this period to about 125 C. The temperature rise was controlled by allowing the xylene to reflux over and to separate out the xylene by a phase separating trap. In any event, the temperature was raised shortly to 138-140 C. and allowed to reflux at this temperature for almost three hours. Tests indicated that the reaction was complete at the end of this time; in fact, it probably was complete at a considerably earlier stage. The xylene which had been separated out was returned to the mixture so that the reaction mass at the end of the procedure represented about 50% reaction product and 50% solvent. The procedure employed is, of course, simple in light of what has been said previously; in fact, it corresponds to the usual procedure employed in connection with an oxyalkylating agent such as glycide, i.e., a non-volatile oxyalkylating agent. At the end of the reaction period the mass obtained was a dark, viscous mixture. It could be bleached, of course, by use of charcoal, filtering earths, or the like.

Various examples obtained in substantially the samemanner as employed are described in the following table:

TABLE VIII Xy- Gatalyst- Time of Max. E21 alkyl- Amt., Diepox- Amt., (NaOCHa), Xylene, Molar reaction, temp., Color and physical state No ate d gms. ide used gms. 7 grams gms. ratio hrs. C.

217 3A 17 1.1 234 2:1 3 140 Dark, viscous mass. 400 3A 17 2.4 477 2:1 4 145 Do. 247 3A 17 1.3 264 2:1 3 150 Do 509 311 17 3.1 520 2:1 4 148 Do 249 3A 17 1.3 266 2:1 2.5 150 Do 402 3A 17 2.0 419 2:1 4 145 Do 708 3A 17 3.5 725 2:1 5 152 Do 192 3.4 17 1.0 209 2:1 25 142 Do 319 3A 17 1.0 336 2:1 3 147 Do 249 3A 17 1.2 250.7 2:1 3 155 Do 217 B1 27.5 1.2 244.5 2:1 3.5 145 Do 400 B1 27.5 2.4 487.5 2:1 4 150 Do. 247 B1 27.5 1.3 274.5 2:1 4 152 Do. 500 B1 27.5 3.1 035.5 2:1 5 158 Do. 249 B1 27.5 1.3 275.5 2:1 4 140 D0. 402 B1 27.5 1.2 420.5 2:1 5 150 Do 703 B1 27.5 2.0 735.5 2:1 5. 152 Do 192 B1 27.5 1.0 210.5 2:1 3.5 148 D0. 310 B1 27.5 1.7 340.5 2:1 4 150 Do. 240 B1 2.8 1.2 251.8 2:1 3 152 Do TABLE 1X Reference to the 4:3 ratio means there can be some Probable variation within reasonable limits, for instance, several Oxyalkylated molecular Amount of Amount of P Q t 1 1 y or other- In other d w could @5111 Weigh? Product use, for example, 3.9 or 4.1 moles instead of 4 moles, or

used reaction grams grams r product one might use 2.9 or 3.1 moles 1nstead of 3 moles. As the molal ratio of the polyepoxide to oxyalkylated resin 4,680 4,680 2,340 increases, i.e., approaches a 1:1 ratio there is greater 2: opportunity for cross-linking or side reactions; or stated 12; 520 0: 250 31130 another way, gelation is more apt to take place. This is 3 2 238 2 58 true of a polyepoxide which includes free hydroxyl groups 141 500 71 250 a: to a greater degree than one which does not contain free ,180 4,105 e, 720 5. 720 a, 350 hydroxyl groups- 50,100 5, 010 2.50;; We have found no difliculty particularly if the tem- 3' $58 $23 perature range is kept lower than in the preparation of 5,49 5, 490 2, 745 15 the intermediates, i.e., if in the 2-step process a tempera- 23 g: g; ture range of 80 C. to 90 C. is used in a later stage 2. g g g. 522 g. Egg and preferably if this temperature is used even in the prep- 41390 41385 2:199 aration of intermediates, i.e., the 2:1 ratio reactant. 6.930 6.930 3.465 Everything else being equal additional solvent tends to 50, 370 5, 040 2, 520

reduce cross-linking and, in any event, when the reacuon In some instances there seems to be a change takes place after the intermediate is allowed to stand for some period of time with the residual catalyst present. The nature of this change is not well defined but it may be due to the fact that there is present a small amount of the polyepoxide unreacted, which reacts slowly. As a rule, when the intermediate is to be stored for a period of time and then perhaps subjected to reaction with the same poly-. epoxide or perhaps a different polyepoxide of the same general kind, we prefer to neutralize the added caustic by the addition of a small amount of hydrochloric acid, sulphuric acid, phosphoric acid or an organic acid such as toluene sulfonic acid. A polydecylated benzene silphonic is suitable.

If the intermediate is to be converted immediately from the 2:1 ratio to the 4:3 ratio then in that event there is no need to neutralize the catalyst present. Indeed, such catalyst is taken into consideration in calculating the amount of catalyst present. In other words, one need not add as much catalyst when the residual catalyst is present as one Would have to add if it had been previously neutralized.

is complete it is preferable to eliminate alkalinity in the manner described above.

Example 1g This is merely a continuation so as to change the reactant ratio in a previous derivative, to wit, Example le, described above. Example 1e, and other comparable compounds are conveniently referred to as polyepoxidederived intermediate products. In any event, 234 grams of this material dissolved in 246 grams of xylene, along with a total of 25 grams of sodium methylate as a catalyst, were treated in exactly the same manner as previously described, with 8.5 grams of dliepoxide 3a. This 50 Similar derivatives were obtained using other intermediates and also using diepoxide B1 previously described, all of which is summarized in the two tables following, to wit, Tables X and XI.

TABLE X Polyepoxide Catalyst- Time of Max. Ex. N0. derived inter- Amt., PlGpOX- Amt., (NaOOHa), Xylene, Molar reaction, temp., Color and physical mediatetpr0d gms. ide used gms. grams gms. ratio hrs. "0 state 234 3A 8. 5 2. 5 246 2:1 1 Dark viscous mass. 477 3A 8. 5 4. 9 485 2:1 1 82 Do. 264 3A 8. 5 2. 7 272 2:1 1 80 D0. 250 3A 3. 4 2. 5 253 2:1 1 85 D0. 266 3A 8. 5 2.7 274 2:1 1 80 D0. 419 3A 8. 5 4. 3 427 2: 1 1 80 Do, 290 3A 3. 4 2. 9 293 2: 1 1 80 D0; 209 3A 8.5 2. 2 217 2: l 1 81 D0. 336 3A 8. 5 3. 4 344 2:1 1 80 Do.

TABLE XCntinued Polyepoxide Catalyst- Time of Max. Ex. No. derived intor- Amt, Diepox- Amt, (NEOCI'IQ), Xylene, Molar reaction, temp, Color and physical mediate prodgms. ide used grns grams gms. ratio hrs. "0 state not 501 3A 1.7 5.0 503 2:1 1 80 Do. 234 B1 13.8 2.5 248 2:1 1 so Do. 477 B1 12.8 4.9 491 2:1 1 82 Do. 204 B1 13.8 2.8 275 2:1 1 84 D0. 250 B1 5.5 2.0 255 2:1 1 00 Do. 200 B1 13.3 2.8 230 2:1 1 00 D0. 410 B1 13.8 4.3 433 2:1 1 85 Do. 200 B1 5.5 2. 0 205 2:1 1 80 Do. 209 B1 13.3 2.2 223 2:1 1 so D0. 530 B1 13.8 3.5 1450 2:1 1 s2 Do. 501 B1 2.8 5.0 504 2:1 1 80 Do.

TABLE XI Example Igg Probable ne-5f i1 Oxyalkylated molecular Amount ol Amountof T 3 1b a pmcedj'ue, which 1 essence produciis Ex. No. resin wt. o1 product, solvent, the same end products as 111 the case of Example 1g in used grams grams Table X, preceding. 217 grams of the oxyalkylated resin previously ldentified as Example 211, were reacted with 9,700 4,850 2425 41.5 grams of diepoxide B]. The amount of catalyst used @22 @3332 was 1.3 grams of sodium methylatc. The amount of 251350 2152s 1200 Xylene used was 244.5 grams. The molal ratio of oxyt' 4 a n 38 alkylated resin to d1epox1de was 4:3. The reaction time 20.340 5,808 2.934 was approximately 4.5 hours. The maximum temperas, 700 4,350 2,175 1 12,780 2,756 1,378 tu1e employed was 83 C. The end product, of course, 8 238 was substantially the same as that obtained under the 201050 41010 21005 heading of Example 1g, preceding. For this reason no r zbig g: g: add1t1onal data are 1ncluded 1n regard to probable molec- %%,%8 ular weight, etc., as appeared in Table XI, for the reason ,Ifi 20,070 5, 004 21907 that it is 1n essence rdenncal as far as Example 1g is cong cerned and similarly, the data in regard to Example Zgg I I i I a I a 101, 200 5,004 2, 532 in Table XII are substantially idenncal 1n regard to Example 2g in Table XI.

TABLE XII Oxy- Catalyst Time of Max. Ex. alkyl- Amt, Diepox' Arut (N20011:), Xylene, Molar reaction, temp., Color and physical state No. ated gms. ide used gms. grams gms. ratio hrs. C.

217 131 41.5 1.3 244.5 4:3 4.4 83 Dark viscous mass. 400 B1 41.5 2.5 487.5 4:3 5.5 34 D0. 247 B1 41.5 1.5 274.5 4:3 0.0 80 D0. 000 B1 41.5 3.3 0305 4:3 5.5 as Do. 240 B1 41.5 1.5 270.5 4:3 4.8 81 D0. 402 B1 41.5 1.4 429.5 4:3 4.0 82 D0. 708 B1 41.5 2.0 735.5 4:3 0.1 82 Do. 192 B1 41.5 1.3 319.5 4:3 5.0 83 Do. 1 310 B1 41.5 1.0 340.5 4:3 5.0 35 Do. 249 B1 4.10 1.4 251.8 4:3 4.0 07 D0. 1

PART 6 PART 7 S bdi i i B 69 As to the use of conventional demulsifying agents reference is made to US. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and eifect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Examples 1g or lg herein described.

As previously noted, there is no need to employ a 2-stage procedure except to the extent that it is convenient. For instance, it would be convenient if a different polyepoxide were used in the second stage. However, as 70 far as employing the 4:3 ratio of reactants instead of the 2:1 as a single step, it seems no description is neces sary because the procedure would be obvious in light of what has been said. Purely, as an illustration, :1. number RT 3 of examples will be included. The products, compounds, or the like herein described 25 can be employed for various purposes and particularly for the resolution of petroleum emulsions of the Water-inoil type as described in detail in Part 7 immediately preceding.

Such products can be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cation active materials. Instead of an imine, one may employ what is a somewhat equivalent material, towit, a dialkylaminoepoxypropane of the structure wherein R and R" are alkyl groups.

it is not necessary to point out that after reaction with a reactant of the kind described which introduces a basic nitrogen atom that the resultant product can be employed for the resolution of emulsions of the water-in-oil type as described in Part 7, preceding, and also for other purposes described hereinafter.

Referring now to the use of the products obtained by reaction with a polyepoxide and certain specified oxyalkylated products obtained in the manner described in Part 6 preceding, it is to be noted that in addition to their use in the resolution of petroleum emulsions they may be used as emulsifying agents for oils, fats, and waxes; as ingredients in insecticide compositions; or as detergents and wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have utility as such but they can serve as initial materials for more complicated reactions of the kind ordinarily requiring a hydroxyl radical. This includes esterification, etherization, etc.

The oxyalkylated derivatives may be used as valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous and nonaqueous types. They may be used in connection with other processes where they are injected into an oil or gas Well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood Waters. These derivatives also are suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initial resin, the particular monoepoxide selected, and the ratio of monoepoxide to resin, together with the particular polyepoxide employed, result in a variety of materials which are useful as wetting agents or surface tension reducing agents; as detergents, emulsifiers or dispersing agents; as additives for lubricants, both of the natural petroleum type and the synthetic type; as additives in the flotation of ores, and at times as aids in chemical reactions in so far that dernulsification is produced between the insoluble reactants. Furthermore, such products can be used for a variety of other purposes, including use as corrosion inhibitors, deioamers, asphalt additives and at times even in the resolution of oil-inwater emulsions. They serve at times as mutual solvents promoting a homogeneous system from two otherwise insoluble phases.

Having thus described our invention, what We claim as new and desired to secure by Letters Patent is:

1. The products obtained by reacting (A) an oxyalkylated phenol-aldehyde resin containing a plurality of active hydrogen atoms, and (B) a phenolic polyepoxide containing at least two 26 l,2-epox'y rings free from reactive functional groups other than 1,2-epoxy and hydroxyl groups, and cogenerically associated compounds formed in the preparation of said polyepoxides; said epoxides being monomers and low molal polymers not exceeding the tetramers; said epoxides being selected from the class consisting of "((1) compounds where the phenolic nuclei are di rectly joined without "an intervening bridge radical, and (b) compounds containing a radical in which two phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone resi dues formed by the elimination of the ket'onic oxygen atom, and aldehyde residues obtained by the elimination of the aldehyde "oxygen atom, the divalent radical the divalent radical, the divalent sul'fone radical, and the divalent mono-sulfide radical --S--, the divalent radical and the 'divalent disulfide radial -S-S--; said phenolic portion of the diepoxide being obtained from a phenol of the structure in which R, R, and R' represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; said oxyalkylated phenol-aldehyde resins reactant (A), being the products derived by oxyalkylation of (aa) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (bb) a fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is selected from the group consisting of phenyl and saturated hydrocarbon radicals having not more than 24 carbon atoms and sub stituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R O) in which R is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n" is a numeral varying from 1 to with the proviso that at least 27 2 moles of alkylene oxide be introduced for each phenolic nucleus, and that the resin by weight represent at least 2% of the oxyalkylated derivative; the ratio of reactant (A) to reactant (B) being in the proportion of four moles of (A) and three moles of (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of nonthermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

2. The products obtained by reacting (A) an oxyalkylated phenol-aldehyde resin containing a plurality of active hydrogen atoms, and (B) a compound consisting essentially of the following formula with the proviso that (B) consist principally of the monomer as distinguished from other cogeners; said oxyalkylated phenol-aldehyde resins being the products derived by oxyalkylation of (aa) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide,

butylene oxide, glycide and methylglycide, and

(bb) an oxyalkylation-susceptible fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction be tween a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is selected from the group consisting of phenyl and saturated hydrocarbon radicals having not more than 24 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R O) in which R is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 120; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus, and that the resin by weight represent at least 2% of the oxyalltylated derivative; the ratio of reactant (A) to reactant (B) being in the proportion of four moles of (A) to three moles of (B); 25 With the further proviso that said reactive compounds (A) and (B) be members of the class consisting of nonthermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

35 References Cited in the file of this patent UNITED STATES PATENTS 

1. THE PRODUCTS OBTAINED REACTING (A) AN OXYALKLATED PHENOL-ALDEHYDE RESIN CONTAINING A PLURALITY OF ACTIVE HYDROGEN ATOMS, AND (B) A PHENOLIC POLYOXIDE CONTAINING AT LEAST TWO 1,2-EPOXY RINGS FREE FROM REACTIVE FUNCTIONAL GROUPS OTHER THAN 1,2-EPOXY AND HYDROXYL GROUPS, AND COGENERICALLY ASSOCIATED COMPOUNDS FORMED IN THE PREPARATION OF SAID POLYOXIDES; SAID EPOXIDES BEING MONOMERS AND LOW MOLAL POLYMERS NOT EXCEEDING THE TETRAMERS; SAID EPOXIDES BEING SELECTED FROM THE CLASS CONSISTING OF (A) COMPOUNDS WHERE THE PHENOL NUCLEI ARE DIRECTLY JOINED WITHOUT AN INTERVENING BRIDGE RADICAL, AND (B) COMPOUNDS CONTAINING A RADICAL IN WHICH TWO PHENOLIC NUCLEI ARE JOINED BY A DIVALENT RADICAL SELECTED FROM THE CLASS CONSISTING OF KETONE RESIDUES FORMED BY THE ELIMINATION OF THE KETONIC OXYGEN ATOMS, AND ALDEHYDE RESIDUES OBTAINED BY THE ELIMINATION OF THE ALDEHYDE OXYGEN ATOM, THE DIVALENT RADICAL 